Fungicidal N-phenylcarbamates

ABSTRACT

Use of an N-phenylcarbamate of the formula: ##STR1## as a fungicidal agent against phytopathogenic fungi, particularly strains which are resistant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides.

This is a continuation-in-part application of our copending application Ser. No. 367,404 filed on Apr. 12, 1982, now U.S. Pat. No. 4,482,546.

This invention relates to fungicidal N-phenyl-carbamates.

Benzimidazole and thiophanate fungicides such as Benomyl (methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate), Fubelidazol (2-(2-furyl)benzimidazole), Thiabendazole (2-(4-thiazolyl)benzimidazole), Carbendazim (methyl benzimidazol-2-ylcarbamate), Thiophanate-methyl (1,2-bis(3-methoxycarbonyl-2-thioureido)benzene), Thiophanate (1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene), 2-(O,S-dimethylphosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene and 2-(O,O-dimethylthiophosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene are known to show an excellent fungicidal activity against various plant pathogenic fungi, and they have been widely used as agricultural fungicides since 1970. However, their continuous application over a long period of time results in phytopathogenic fungi becoming tolerant to the fungicides, whereby their plant disease-preventive effect is much lowered. Further, the fungi which gain tolerance to certain kinds of benzimidazole or thiophanate fungicides also show considerable tolerance to some other kinds of benzimidazole or thiophanate fungicides. Thus, they are apt to obtain crosstolerance. Therefore, if any material decrease of their plant disease-preventive effect in certain fields is observed, their application to such fields has to be discontinued. But, it is often observed that the density of drug-resistant organisms is not decreased even long after the discontinuation of the application. Although other kinds of fungicides have to be employed in such a case, only few are as effective as benzimidazole or thiophanate fungicides in controlling various phytopathogenic fungi. Benzimidazole and thiophanate fungicides are hereinafter referred to as "benzimidzole and thiophanate fungicides". Cyclic imide fungicides such as Procymidone (3-(3',5'-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide), Iprodione (3-(3',5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione), Vinchlozolin (3-(3',5'-(dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione), ethyl (RS)-3-(3',5'-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, particularly those caused by Botrytis cinerea, have the same defects as previously explained with respect to the benzimidazole thiophanate fungicides.

In C.R. Acad. Sc. Paris, t. 289, S'erie D, pages 691-693 (1979), it is described that herbicides such as Barban (4-chloro-2-butynyl N-(3-chlorophenyl)carbamate), Chlorobufam (1-methyl-2-propynyl N-(3-chlorophenyl)carbamate), Chlorpropham (isopropyl N-(3-chlorophenyl)carbamate) and Propham (isopropyl N-phenylcarbamate) exhibit a fungicidal activity against certain organisms tolerant to some of the benzimidazole thiophanate fungicides. However, their fungicidal activity against the drug-resistant fungi is not strong enough, and hence, practically they can not be used as fungicides.

As a result of the study seeking a new type of fungicides, it has now been found that N-phenylcarbamates of the formula: ##STR2## wherein X and Y, which may be the same or different, are each a halogen atom, a lower alkyl group, a lower alkenyl group, a lower cyanoalkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alkyl group substituted with at least one member selected from the group consisting of halogen, hydroxyl and cyano, or a group of the formula: ##STR3## in which R³ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R⁴ and R⁵, which may be the same or different, are each a lower alkyl group, R⁶ is a hydrogen atom or a lower alkyl group, n is 2, 3 or 4; Z is an oxygen atom or a sulfur atom; R¹ a lower alkyl group, a lower alkenyl gruop, a lower alkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, lower alkoxy and lower cycloalkyl and R² is a C₁ -C₈ alkyl group, a C₃ -C₈ alkenyl group, a lower cycloalkyl group, a lower haloalkenyl group, a lower haloalkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, phenoxy, lower aralkyloxy and lower cycloalkyl, show an excellent fungicidal activity against plant pathogenic fungi which have developed resistance to benzimidazole thiophanate fungicides and/or cyclic imide fungicides. It is notable that their fungicidal potency against the organisms tolerant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-resistant fungi" or "drug-resistant strains") is much higher than that against the organisms sensitive to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-sensitive fungi" or "drug-sensitive strains").

All the N-phenylcarbamates (I) are novel compounds except ethyl N-(3,4,5-trimethoxyphenyl)carbamate, ethyl N-(3,4,5-triethoxyphenyl)carbamate, propargyl N-(4-methoxy-3,5-dibromophenyl)carbamate, methyl N-(4-methoxy-3,5-dichlorophenyl)thiolcarbamate, methyl N-(3-bromo-4-methoxy-5-chlorophenyl)thiolcarbamate and 2-butynyl N-(3,4,5-trimethoxyphenyl)carbamate are known. These compounds have been known, but it has not been known or reported that they have fungicidal activity or that they are useful as fungicides [DT-OS No. 2,041,986, French patent M8200, Arch. Pharm., 272, 221-235 (1934)].

Thus, the present invention provides a fungicidal composition which comprises, as an active ingredient, a fungicidally effective amount of the N-phenylcarbamate (I) and an inert carrier or diluent. It also provides a combination composition comprising as active ingredients the N-phenylcarbamate (I) together with a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide, which is fungicidally effective against not only drug-sensitive fungi but also drug-resistant fungi, and hence particularly effective for the prevention of plant diseases. It also provides a method of controlling plant pathogenic fungi including drug-resistant strains and drug-sensitive strains applying a fungicidally effective amount of the N-phenyl-carbamate (I) to plant pathogenic fungi. It further provides novel N-phenylcarbamates which are representable by the formula (I) wherein X, Y, Z, R¹ and R² are each as defined above. It furthermore provides a process for producing the novel N-phenylcarbamates (I), which comprises reacting a 3,4,5-trisubstituted aniline of the formula: ##STR4## wherein X, Y and R¹ are each as defined above, with a chloroformate of the formula: ##STR5## wherein Z and R² are each as defined above (Procedure (a)), or reacting a 3,4,5-trisubstituted phenyl isocyanate of the formula: ##STR6## wherein X, Y and R¹ are each as defined above, with an alcohol or thiol of the formula:

    HZR.sup.2                                                  (V)

wherein Z and R² are each as defined above (Procedure (b)). Moreover, it provides a process for producing the N-phenylcarbamates of the formula (I) wherein at least one of X and Y is a hydroxyiminomethyl group or a lower alkoxyiminomethyl group, which comprises reacting a benzaldehyde of the formula: ##STR7## wherein Y, Z, R¹ and R² are each as defined above, with hydroxyamine or lower alkoxyamine (Procedure (c)).

The term "lower" used hereinabove and hereinafter in connection with organic radicals or compounds indicates that such radicals or compounds each have not more than 6 carbon atoms. Preferable X and Y are fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, n-butyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, hydroxymethyl, cyanomethyl, 2-cyanoethyl, 2-cyanovinyl, methoxymethyl, ethoxymehyl, allyloxymethyl, propargyloxymethyl, 2-fluoroethoxymethyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, 2-fluoroethoxycarbonyl, propargyloxycarbonyl, dimethoxymethyl, idethoxymethyl, ethylenedioxymethyl, formyl, acetyl, hydroxyiminomethyl, methoxyiminomethyl, carbamoyl or N-methylcarbamoyl. Particularly preferred X and Y are fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, methoxymethyl, methoxycarbonyl, dimethoxymethyl, diethoxymethyl, acetyl or methoxyiminomethyl. Especially active are those compounds wherein X and Y are each fluorine, chlorine, bromine, methoxymethyl, methyl, ethyl or n-propyl, and those compounds wherein X is fluorine, chlorine, bromine, methoxy or ethoxy and Y is chlorine, bromine, methyl, ethyl, n-propyl, methoxy, ethoxy, cyano, methoxymethyl, methoxycarbonyl, dimethoxymethyl or acetyl. Preferred Z is oxygen. Preferable R¹ is methyl, ethyl, n-propyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl or cyclopropylmethyl. Particularly preferable R¹ is methyl, ethyl, allyl, propargyl, difluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl. Most preferable R¹ is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl. Preferable R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylheptyl, 1-methyl-2-propenyl, propargyl, 2-butenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 1-butyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, 2-cyanoethyl, 2fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-bromomethylpropyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butenyl, 4-chloro-2 -butynyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-methoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-n-butoxyethyl or 1-methyl-2-phenoxyethyl. Particularly preferable R² is methyl, ethyl, isopropyl, sec-butyl, 1-ethylpropyl, allyl, 1-methyl-2-propenyl, 2-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 1-methyl-3-butynyl, 2-cyanoethyl, 2-fluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 2-(2-chloroethoxy)-ethyl, 1-methyl-2-methoxyethyl or 1-methyl-2-n-butoxyethyl. Most preferable R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, 1-methyl-2-propynyl, propargyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1methyl-2-methoxyethyl.

The N-phenylcarbamates (I) are fungicidally effective against a wide scope of plant pathogenic fungi, of which examples are as follows: Podosphaera leucotricha, Venturia inaequalis, Mycosphaerella pomi, Marssonina mali and Sclerotinia mali of apple, Phyllactinia Kakicola and Gloeosporium kaki of persimmon, Cladosporium carpophilum and Phomopsis sp. of peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina and Glomerella cingulata of grape, Cercospora beticola of sugarbeet, Cercospora arachidicola and Cercospora personata of peanut, Erysiphe graminis f. sp. hordei, Cercosporella herpotrichoides and Fusarium nivale of barley, Erysiphe graminis f. sp. tritici of wheat, Sphaerotheca fuliginea and Cladosporium cucumerinum of cucumber, Cladosporium fulvum of tomato, Corynespora melongenae of eggplant, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae of strawberry, Botrytis alli of onion, Cercospora apii of cerely, Phaeoisariopsis griseola of kidney bean, Erysiphe cichoracearum of tobacco, Diplocarpon rosae of rose, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum of orange, Botrytis cinerea of cucumber, eggplant, tomato, strawberry, pimiento, onion, lettuce, grape, orange, cyclamen, rose or hop, Sclerotinia sclerotiorum of cucumber, eggplant, pimiento, lettuce, celery, kidney bean, soybean, azuki bean, potato or sunflower, Sclerotinia cinerea of peach or cherry, Mycosphaerella melonis of cucumber or melon, etc. Namely, the N-phenylcarbamates (I) are highly effective in contolling the drug-resistant strains of said fungi.

The N-phenylcarbamates (I) are also fungicidally effective against fungi sensitive to said known fungicides as well as fungi to which said known fungicides are ineffective. Examples of such fungi are Pyricularia oryzae, Pseudoperonospora cubensis, Plasmopara, viticola, Phytophthora infestans, etc.

Advantageously, the N-phenylcarbamates have low toxicity and have little detrimental action on mammals, fish and so on. Also, they may be applied to an agricultural field without causing any material toxicity to important crop plants.

In view of their excellent fungicidal properties, particularly useful are the compounds of the formula (I) wherein X and Y are independently fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, n-butyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, hydroxymethyl, cyanomethyl, 2-cyanoethyl, 2-cyanovinyl, methoxymethyl, ethoxymethyl, allyloxymethyl, propargyloxymethyl, 2-fluoroethoxymethyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, 2-fluoroethoxycarbonyl, propargyloxycarbonyl, dimethoxymethyl, diethoxymethyl, ethylenedioxymethyl, formyl, acetyl, hydroxyiminomethyl, methoxyiminomethyl, carbamoyl or N-methylcarbamoyl, Z is oxygen or sulfur, R¹ is methyl, ethyl, n-propyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifloroethyl, 2-methoxyethyl or cyclopropylmethyl, R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylheptyl, 1-methyl-2-propenyl, propargyl, 2-butenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, 1-methyl-2-propynyl, 1-ethyl-b 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 1-butyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, 2-cyanoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-bromomethylpropyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butenyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-methoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-n-butoxyethyl or 1-methyl-2-phenoxyethyl. Preferred are the compounds of teh formula (I) wherein X and Y are independently fluorine, chlorine, bromine, iodine, methy, ethyl, n-propyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, methoxymethyl, methoxycarbonyl, dimethoxymethyl, diethoxymethyl, acetyl or methoxyiminomethyl, Z is oxygen, R¹ is methyl, ethyl, allyl, propargyl, difluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methyl-2-propenyl, 2-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 1-methyl-3-butynyl, 2-cyanoethyl, 2-fluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 2-(2-chloroethoxy)ethyl, 1-methyl-2-methoxyethyl or 1-methyl-2-n-butoxyethyl.

Particularly preferred are the compounds of the formula (I) wherein X and Y are each fluorine, chlorine, bromine, methoxymethyl, methyl, ethyl or n-propyl, Z is oxygen, R¹ is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl and R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl and the compounds of the formula (I) wherein X is fluorine, chlorine, bromine, methoxy or ethoxy, Y is chlorine, bromine, methyl, ethyl, n-propyl, methoxy, ethoxy, cyano, methoxymethyl, methoxycarbonyl, dimethoxymethyl or acetyl, Z is oxygen, R¹ is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl and R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl.

More preferred are the compounds of the formula (I) wherein X and Y are each chlorine, methyl or methoxymethyl, Z is oxygen, R¹ is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, preferably ethyl, and R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl and the compounds of the formula (I) wherein X is fluorine, chlorine, bromine, methoxy or ethoxy, Y is chlorine, methyl, methoxycarbonyl, methoxymethyl or cyano, Z is oxygen, R¹ is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, preferably ethyl, and R² is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl. Most preferred are the followings:

Isopropyl N-(3,5-dichloro-4-ethoxyphenyl)carbamate;

Isopropyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;

Propargyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;

1-Methyl-2-propenyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;

1-Methyl-2-propynyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;

1-Methyl-2-methoxyethyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;

Isopropyl N-[3,5-dimethyl-4-(2-propynyloxy)phenyl]carbamate;

Isopropyl N-(3-chloro-4-ethoxy-5-methoxyphenyl)carbamate;

Methyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

Ethyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

Isopropyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

sec-Butyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

Allyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

Propargyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

1-Methyl-2-propenyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

1-Methyl-2-propynyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

4-Chloro-2-butynyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

2-Cyanoethyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;

Isopropyl N-[3-chloro-5-ethoxy-4-(2-propenyloxy)phenyl]carbamate;

1-Methyl-2-methoxyethyl N-[3-chloro-5-ethoxy-4-(2-propenyloxy)phenyl]carbamate;

Isopropyl N-[3-chloro-5-ethoxy-4-(2-propynyloxy)phenyl]carbamate;

Isopropyl N-[3-chloro-4-(2-chloroethyloxy)-5-ethoxyphenyl]carbamate;

Isopropyl N-(3-methoxy-4-ethoxy-5-methylphenyl)carbamate;

Methyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

Ethyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

sec-Butyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

Propargyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

1-Methyl-2-propenyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

1-Methyl-2-propynyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

1-Methyl-2-methoxyethyl N-(3,4-diethoxy-5-methylphenyl)carbamate;

4-Chloro-2-butynyl N-(3,4-diethyoxy-5-methylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-ethylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-vinylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-methoxyphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-methoxymethylphenyl)carbamate;

1-Methyl-2-methoxyethyl N-(3,4-diethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-methoxycarbonylphenyl)carbamate;

Isopropyl N-(3-cyano-4,5-diethoxyphenyl)carbamate;

Isopropyl N-(3-methyl-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-methyl-4-ethoxy-5-n-propylphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-bromophenyl)carbamate;

Isopropyl N-(3-methyl-4-propynyloxy-5-ethoxyphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-acetylphenyl)carbamate;

Isopropyl N-[3,4-diethoxy-5-(1,2-dibromoethyl)phenyl]carbamate;

Isopropyl N-(3-chloro-4-propynyloxy-5-methoxyphenyl)carbamate;

Isopropyl N-(3,4-diethoxy-5-dimethoxymethylphenyl)carbamate;

Isopropyl N-(3-chloro-4-ethoxy-5-n-propylphenyl)carbamate;

Isopropyl N-(3-bromo-4-ethoxy-5-methoxyphenyl)carbamate;

Isopropyl N-(3,5-diethyl-4-ethoxyphenyl)carbamate;

Isopropyl N-(3-chloro-4-ethoxy-5-methylphenyl)carbamate;

Isopropyl N-(3-methyl-4-ethoxy-5-allylphenyl)carbamate;

Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)carbamate;

Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)carbamate;

Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)carbamate;

Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate;

Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate;

Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)carbamate;

Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)carbamate;

Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)carbamate;

Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate;

Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate;

Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)carbamate;

Isopropyl N-([3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]carbamate; etc.

The N-phenylcarbamates (I) can be prepared by either one of the following procedures:

Procedure (a):

Reaction of the 3,4,5-trisubstituted aniline (II) with the chloroformate (III).

The reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide). When desired, the reaction may be performed in the presence of a dehydrohalogenating agent (e.g. pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide) so as to obtain the objective compound (I) in a high yield. The reaction may be accomplished at a temperature of 0° to 150° C. instantaneously or within 12 hours.

Procedure (b):

Reaction of the 3,4,5-trisubstituted phenyl isocyanate (IV) with the alcohol or thiol (V).

The reaction is usually carried out in the absence or presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform, carbon tetrachloride). When desied, a catalyst (e.g. triethylamine, diethylaniline, 1,4-diazabicyclo(2,2,2)octane) may be used. The reaction is normally accomplished at a temperature of 0° to 50° C. instantaneously or within 12 hours.

In case of the N-phenylcarbamates of the formula (I) wherein at least one of X and Y is a hydroxyiminomethyl group or a lower alkoxyiminomethyl group, it may be prepared by the following procedure (Procedure (c)): reacting the benzaldehyde (VI) with an equimolar or excess amount of hydroxylamine or lower alkoxyamine in an inert solvent (e.g. methanol, ethanol). The reaction may be brought to completion in about 0.5 to 12 hours. For preparation of the N-phenylcarbamates of the formula (I) wherein both of X and Y are hydroxyiminomethyl groups or lower alkoxyiminomethyl groups, there may be used as the starting material the benzaldehyde of the formula (VI) wherein Y is a formyl group.

The 3,4,5-trisubstituted aniline (II) used as the starging material in Procedure (a) can be prepared by reducing a nitrobenzene of the formula: ##STR8## wherein X, Y and R¹ are each as defined above, which is obtainable by reacting a nitrophenol of the formula: ##STR9## wherein X and Y are each as defined above with a reagent of the formula: A--R¹ wherein A is a tosyloxy or mesyloxy group or a halogen atom and R¹ is as defined above.

The reaction of the nitrophenol (VIII) with the reagent may be carried out in an inert solvent such as water, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, tetrachloromethane, ethyl acetate, ethanol, isopropanol or dimethylformamide, when desired, in the presence of a base such as pyridine, triethylamine, sodium hydroxide, potassium hydroxide or sodium carbonate. If necessary, the reaction mass may be heated or cooled. The reaction may be accomplished within 0.5 to 12 hours to give the objective compound in a high yield.

The reduction of the nitrobenzene (VII) is usually carried out by a conventional reduction technique such as catalytic reduction with platinum oxide, Raney nickel, platinum black or palladium on carbon, reduction in acidic media, for example, in water containing hydrogen chloride, sulfuric acid or acetic acid, using tin, stannous chloride or iron, or reduction in basic media, for example, in methanol or ethanol, using sodium sulfide or sodium hydrosulfide.

The nitrophenol (VIII) can be prepared by a known method [Bavin and Scott: Can. J. Chem., 36, 1284 (1958)].

The 3,4,5-trisubstituted phenyl isocyanate (IV) emplyed as the starting material in Procedure (b) may be prepared by reacting the 3,4,5-trisubstituted aniline (II) with phosgene. This reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, ethyl acetate) at a temperature of 50° C. to the refluxing temperature of the solvent. The reaction may be accomplished instantaneously or within 12 hours.

The procedures for preparation of the N-phenylcarbamates (I) are illustratively shown in the following Examples.

EXAMPLE 1

Preparation of isopropyl N-(3,5-dichloro-4-methoxyphenyl)carbamate according to Procedure (a):

3,5-Dichloro-4-methoxyaniline (1.8 g) and diethylaniline (1.5 g) were dissolved in benzene (20 ml). To the resultant solution was dropwise added isopropyl chloroformate (1.2 g) in 5 minutes under ice-cooling. After being allowed to stand at room temperature for 12 hours, the reaction mixture was poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of benzene and tetrahydrofuran as the eluent to give isopropyl N-(3,5-dichloro-4-methoxyphenyl)carbamate (Compound No. 2) (2.4 g) in a yield of 91.8%. M.P., 107.5°-108° C.

Elementary analysis: Calcd. for C₁₁ H₁₃ Cl₂ NO₃ : N, 5.02%; C, 47.38%; H, 4.69%; Cl, 25.44%. Found: N, 5.11%; C, 47.52%; H, 4.76%; Cl, 25.49%.

EXAMPLE 2

Preparation of isopropyl N-(3-bromo-5-chloro-4-methoxyphenyl)carbamate according to Procedure (b):

A mixture of 3-bromo-5-chloro-4-methoxyaniline (13.0 g) in toluene (100 ml) was dropwise added to a toluene solution containing 20 g of phosgene at 10° to 20° C. The resulting mixture was gradually heated and, after being refluxed for 30 minutes, cooled to room temperature. The solvent was removed by distillation under reduced pressure to give 3-bromo-5-chloro-4-methoxyphenyl isocyanate (14.4 g). The thus obtained crude substance was added to an isopropanol solution (50 ml) containing triethylamine (1 g). The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of benzene and tetrahydrofuran as the eluent to give isopropyl N-(3-bromo-5-chloro-4-methoxyphenyl)carbamate (Compound No. 33) (16.4 g) in a yield of 92% (calculated from the starting 3-bromo-5-chloro-4-methoxyaniline). M.P., 112°-113.5° C.

Elementary analysis: Calcd. for C₁₁ H₁₃ NO₃ BrCl: N, 4.33%; C, 40.87%; H, 4.05%; Br, 24.72%; Cl, 10.97%. Found: N, 4.35%; C, 40.84%; H, 3.91%; Br, 25.06%; Cl, 11.20%.

EXAMPLE 3

Preparation of isopropyl N-(3-ethyl-4-ethoxy-5-chlorophenyl)carbamate according to Procedure (a):

3-Ethyl-4-ethoxy-5-chloroaniline (1.9 g) and diethylaniline (1.5 g) were dissolved in toluene (20 ml). To the resultant solution was dropwise added isopropyl chloroformate (1.2 g) in 5 minutes under ice-cooling. After being allowed to stand at room temperature for 12 hours, the reaction mixture was poured into ice-water and extracted with toluene. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using toluene as the eluent to give isopropyl N-(3-ethyl-4-ethoxy-5-chlorophenyl)carbamate (Compound No. 53) (2.4 g) in a yield of 89%. M.P., 79°-80.5° C.

Elementary analysis: Calcd. for C₁₄ H₂₀ NO₃ Cl: N, 4.89%; C, 58.69%; H, 7.04%; Cl, 12.38%. Found: N, 4.88%; C, 58.43%; H, 6.97%; Cl, 12.28%.

EXAMPLE 4

Preparation of isopropyl N-(3-ethyl-4-ethoxy-5-methylphenyl)carbamate according to Procedure (b):

A mixture of 3-ethyl-4-ethoxy-5-methylaniline (1.8 g) in toluene (20 ml) was dropwise added to a toluene solution containing 10 g of phosgene at 10° to 20° C. The resulting mixture was gradually heated and, after being refluxed for 30 minutes, cooled to room temperature. The solvent was removed by distillation under reduced pressure to gove 3-ethyl-4-ethoxy-5-methylphenyl isocyanate (2.1 g). The thus obtained crude substance was added to an isopropanol solution (20 ml) containing triethylamine (1 g). The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with toluene. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using toluene as the eluent to give isopropyl N-(3-ethyl-4-ethoxy-5-methylphenyl)carbamate (Compound No. 93) (2.4 g) in a yield of 91% (calculated from the starting 3-ethyl-4-ethoxy-5-methylaniline). M.P., 68°- 69.5° C.

Elementary analysis: Calcd. for C₁₅ H₂₃ NO₃ : N, 5.28%; C, 67.89%; H, 8.74%. Found: N, 5.21%; C, 67.85%; H, 8.96%.

EXAMPLE 5

Preparation of isopropyl N-(3,4-diethoxy-5-methoxyiminomethylphenyl)carbamate according to Procedure (c):

Isopropyl N-(3,4-diethoxy-5-formylphenyl)carbamate (0.6 g) was dissolved in ethanol (20 ml). To the solution was added an aqueous solution (10 ml) containing sodium hydroxide (0.32 g) and methoxyamine hydrochloride (0.66 g). After being allowed to stand for 12 hours, the reaction mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate. The resultant solution was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was washed with hexane to give isopropyl N-(3,4-diethoxy-5-methoxyiminomethylphenyl)carbamate (Compound No. 191) (0.61 g) in a yield of 93%. M.P., 110°-111.5° C.

Elementary analysis: Calcd. for C₁₆ H₂₄ N₂ O₅ : C, 59.24%; H, 7.46%; N, 8.64%. Found: C, 59.01%; H, 7.56%; N, 8.34%.

According to either one of the above Procedures (a), (b) or (c), the N-phenylcarbamates of the formula (I) as shown in Table 1 can be prepared.

                                      TABLE 1                                      __________________________________________________________________________      ##STR10##                                                                     Com-                                                                           pound                                                  Physical                No. X           Y           R.sup.1    R.sup.2       Z constant                __________________________________________________________________________      1  Cl          Cl          CH.sub.3   C.sub.2 H.sub.5                                                                              O M.P.                                                                           94-95.5°                                                                C.                       2  Cl          Cl          CH.sub.3                                                                                   ##STR11##    O M.P. 107.5-108.degr                                                            ee. C.                   3  Cl          Cl          CH.sub.3                                                                                   ##STR12##    O M.P. 75.5-76.degree                                                            . C.                     4  Cl          Cl          CH.sub.3                                                                                   ##STR13##    O M.P. 85-86.5.degree                                                            . C.                     5  Cl          Cl          CH.sub.3   CH.sub.2 C CH O M.P.                                                                           123-124.5°                                                              C.                       6  Cl          Cl          CH.sub.3                                                                                   ##STR14##    O M.P. 57-58°                                                             C.                       7  Cl          Cl          CH.sub.3                                                                                   ##STR15##    O M.P.                                                                           72-73° C.         8  Cl          Cl          CH.sub.3                                                                                   ##STR16##    O M.P. 61-62°                                                             C.                       9  Cl          Cl          CH.sub.3   CH.sub.2 CHCHCH.sub.3                                                                        O M.P.                                                                           75-76° C.        10  Cl          Cl          CH.sub.3   CH.sub.2 CCCH.sub.3                                                                          O M.P.                                                                           110-111°                                                                C.                      11  Cl          Cl          CH.sub.3   CH.sub.2 CH.sub.2 Cl                                                                         O n .sub.D.sup.24.5                                                              1.5541                  12  Cl          Cl          CH.sub.3   CH.sub.2 CHCHCH.sub.                                                                         O Cl                                                                             n .sub.D.sup.22.0                                                              1.5641                  13  Cl          Cl          CH.sub.3   CH.sub.2CCCH.sub.2 Cl                                                                        O M.P.                                                                           105.5-106.5°                                                             C.                     14  Cl          Cl          CH.sub.3                                                                                   ##STR17##    O n .sub.D.sup.23.0                                                              1.5330                  15  Cl          Cl          C.sub.2 H.sub.5                                                                            ##STR18##    O M.P. 65-65.5.degree                                                            . C.                    16  Cl          Cl          C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                  O M.P.                                                                           90-91° C.        17  Cl          Cl          C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 O(n)C.sub.3                                                  H.sub.7       O n .sub.D.sup.24.5                                                              1.5302                  18  Cl          Cl          C.sub.2 H.sub.5                                                                            ##STR19##    O n .sub.D.sup.24.5                                                              1.5288                  19  Cl          Cl          CH.sub.2 CH.sub.2 CH.sub.3                                                                 ##STR20##    O n .sub.D.sup.24.5                                                              1.5251                  20  Cl          Cl          CH.sub.2 CHCH.sub.2                                                                        ##STR21##    O n .sub.D.sup.20.5                                                              1.5439                  21  Cl          Cl          CH.sub.2 CH.sub.2 OCH.sub.3                                                                ##STR22##    O n .sub.D.sup.20.5                                                              1.5283                  22  Cl          Cl          CH.sub.2 CCH                                                                               ##STR23##    O n .sub.D.sup.20.5                                                              1.5511                  23  Cl          Cl          CH.sub.2 CH.sub.2 CHCH.sub.2                                                               ##STR24##    O n .sub.D.sup.21.3                                                              1.5312                  24  Cl          Cl          CH.sub.2 CH.sub.2 CCH                                                                      ##STR25##    O n .sub.D.sup.21.5                                                              1.5220                  25  Cl          Cl                                                                                          ##STR26##                                                                                 ##STR27##    O n .sub.D.sup.20.5                                                              1.5429                  26  Cl          Cl          CHF.sub.2  CH.sub.3      O M.P.                                                                           100-101°                                                                C.                      27  Cl          Cl          CHF.sub.2  C.sub.2 H.sub.5                                                                              O M.P.                                                                           72-73° C.        28  Cl          Cl          CHF.sub.2                                                                                  ##STR28##    O M.P. 131-132.degree                                                            . C.                    29  Cl          Cl          CHF.sub.2                                                                                  ##STR29##    O M.P. 118-119.degree                                                            . C.                    30  Cl          Cl          CHF.sub.2                                                                                  ##STR30##    O M.P. 114-115.degree                                                            . C.                    31  Cl          Cl          CHF.sub.2  CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           83.5-84.5°                                                              C.                      32  Cl          Cl          CH.sub.2 CF.sub.3                                                                          ##STR31##    O M.P. 133-135.degree                                                            . C.                    33  Cl          Br          CH.sub.3                                                                                   ##STR32##    O M.P. 112-113.5.degr                                                            ee. C.                  34  Br          Br          CH.sub.3   CH.sub.3      O M.P.                                                                           111-112°                                                                C.                      35  Br          Br          CH.sub.3   C.sub.2 H.sub.5                                                                              O M.P.                                                                           109.5-111°                                                              C.                      36  Br          Br          CH.sub.3                                                                                   ##STR33##    O M.P. 122.5-124.degr                                                            ee. C.                  37  Br          Br          CH.sub.3   CH.sub.2 CCH  O M.P. 114.5-115.degr                                                            ee. C.                  38  Br          Br          CH.sub.3                                                                                   ##STR34##    O M.P. 56-57.5.degree                                                            . C.                    39   Br         Br          CH.sub.3                                                                                   ##STR35##    O M.P. 78.5-81.5.degr                                                            ee. C.                  40  Br          Br          CH.sub.3   CH.sub.2 CHCHCH.sub.3                                                                        O M.P.                                                                           75-76° C.        41  Br          Br          CH.sub.3   CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           112.5-113.5°                                                             C.                     42  Br          Br          CHF.sub.2  CH.sub.3      O M.P.                                                                           84-85° C.        43  Br          Br          CHF.sub.2  C.sub.2 H.sub.5                                                                              O M.P.                                                                           136-137°                                                                C.                      44  Br          Br          CHF.sub.2                                                                                  ##STR36##    O M.P. 157-159.degree                                                            . C.                    45  Br          Br          CHF.sub.2  CH.sub.2 CCH  O M.P.                                                                           123.5-124.5°                                                             C.                     46   Br         Br          CHF.sub.2                                                                                  ##STR37##    O M.P. 135.5-137.degr                                                            ee. C.                  47  Br          Br          CHF.sub.2                                                                                  ##STR38##    O M.P. 140.5-142.degr                                                            ee. C.                  48  Br          Br          CHF.sub.2  CH.sub.2 CHCHCH.sub.3                                                                        O M.P.                                                                           95-97.5°                                                                C.                      49  Br          Br          CHF.sub.2                                                                                  ##STR39##    O M.P. 110-113.5.degr                                                            ee. C.                  50  Br          Br          CHF.sub.2  CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           105-106°                                                                C.                      51  Cl          CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR40##    O M.P. 79.5-80.5.degr                                                            ee. C.                  52  Cl          CH.sub.3    CHF.sub.2                                                                                  ##STR41##    O M.P. 94-95°                                                              C.                     53  Cl          C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR42##    O M.P. 79-80.5.degree                                                            . C.                    54  Cl          CH.sub.2 CH.sub.2 CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            ##STR43##    O M.P. 71.5-72.degree                                                            . C.                    55  CH.sub.3    CH.sub.3    CH.sub.3                                                                                   ##STR44##    O M.P. 89-90°                                                             C.                      56  CH.sub.3    CH.sub.3    CH.sub.3   CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           72-73° C.        57  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.3      O M.P.                                                                           60-61° C.        58  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              O M.P.                                                                           49.5-51°                                                                C.                      59  CH.sub.3    CH.sub.3     C.sub.2 H.sub.5                                                                           ##STR45##    O M.P. 98-99°                                                             C.                      60  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR46##    O M.P. 86-87°                                                             C.                      61  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR47##    O n .sub.D.sup.19                                                                1.5101                  62  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.2 CCH  O M.P.                                                                           110-111°                                                                C.                      63  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 CCH                                                                        O M.P.                                                                           67-68° C.        64  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR48##    O M.P. 83.5-84.5.degr                                                            ee. C.                  65  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR49##    O M.P. 103-104.degree                                                            . C.                    66  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR50##    O M.P. 63.5-65.degree                                                            . C.                    67  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR51##    O M.P. 68.5-69.5.degr                                                            ee. C.                  68  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR52##    O M.P. 75.5-76.5.degr                                                            ee. C.                  69  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 F                                                                          O M.P.                                                                           71-72° C.        70  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR53##    O M.P. 95-96°                                                             C.                      71  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR54##    O M.P. 82-83°                                                             C.                      72  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 OCH.sub.2                                                    CHCH.sub.2    O n .sub.D.sup.19.5                                                              1.5221                  73  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR55##    O n .sub.D.sup.22.5                                                              1.5051                  74  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR56##    O M.P. 82-83°                                                             C.                      75  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR57##    O M.P. 124-125.degree                                                            . C.                    76  CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CCCH.sub.2 Cl                                                                      O M.P.                                                                           107-108°                                                                C.                      77  CH.sub.3    CH.sub.3    CH.sub.2 CHCH.sub.2                                                                        ##STR58##    O n .sub.D.sup.19.6                                                              1.5228                  78  CH.sub.3    CH.sub.3    CH.sub.2 CCH                                                                               ##STR59##    O n .sub.D.sup.22.5                                                              1.5261                  79  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR60##    O M.P. 51-52°                                                             C.                      80  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR61##    O n .sub.D.sup.22                                                                1.4908                  81  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR62##    O n .sub.D.sup.22                                                                1.4976                  82   CH.sub.3   CH.sub.2 CH.sub.2 CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            ##STR63##    O n .sub.D.sup.18.5                                                              1.5127                  83  CH.sub.3    CH.sub.2 CHCH.sub.2                                                                        C.sub.2 H.sub.5                                                                            ##STR64##    O n .sub.D.sup.17.5                                                              1.5205                  84  Br          F           C.sub.2 H.sub.5                                                                            ##STR65##    O n .sub.D.sup.20.5                                                              1.5299                  85  I           I           C.sub.2 H.sub.5                                                                            ##STR66##    O M.P. 107.5-109.degr                                                            ee. C.                  86  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR67##    O M.P. 81-82°                                                             C.                      87  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR68##    O M.P. 60-61°                                                             C.                      88  CH.sub.3    CH.sub.3    CHF.sub.2  CH.sub.2 CCCH.sub.3                                                                          O M.P.                                                                           77-78° C.        89  CH.sub.3    CH.sub.3    CHF.sub.2  CH.sub.2 CH.sub.2 Br                                                                         O M.P.                                                                           99.5-100.5°                                                             C.                      90  CH.sub.3    CH.sub.3    CHF.sub.2  CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           71-73° C.        91  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR69##    O M.P. 91-93°                                                             C.                      92  CH.sub.3    CH.sub.3    CHF.sub.2                                                                                  ##STR70##    O n .sub.D.sup.24.5                                                              1.4965                  93  CH.sub.3    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR71##    O M.P. 68-69.5            94  CH.sub.3    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 F                                                                          O n .sub.D.sup.22.9                                                              1.5122                  95  CH.sub.3    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           CH.sub.2 CF.sub.3                                                                            O M.P.                                                                           80-81.5°                                                                C.                      96  CH.sub.3    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR72##    O M.P. 66-68°                                                             C.                      97  CH.sub.3    C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR73##    O n .sub.D.sup.22.9                                                              1.5149                  98  CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 ##STR74##    O M.P. 68-71°                                                             C.                      99  CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 CH.sub.2 CCH O n .sub.D.sup.24.6                                                              1.5280                  100 CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCHCH.sub.2 Cl                                                                     O n .sub.D.sup.25.0                                                              1.5335                  101 CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CCH                                                                               ##STR75##    O n .sub.D.sup.24.5                                                              1.5235                  102 CH.sub.3    C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2 CHCH.sub.2                                                               ##STR76##    O n .sub.D.sup.23.5                                                              1.5225                  103 CH.sub.3    C.sub.2 H.sub.5                                                                             ##STR77##                                                                                 ##STR78##    O n .sub.D.sup.24.6                                                              1.5262                  104  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           CH.sub.3      O M.P.                                                                           83.5-85°                                                                C.                      105 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR79##    O M.P. 87-89.5.degree                                                            . C.                    106 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           84-86.5°                                                                C.                      107 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2 CCH                                                                      ##STR80##    O n .sub.D.sup.23.5                                                              1.5335                  108 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                                ##STR81##    O M.P.  67-69°                                                             C.                     109 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            CHF.sub.2                                                                                  ##STR82##    O M.P. 89-90°                                                             C.                      110 Cl          OCH.sub.3   C.sub.2 H.sub.5                                                                            ##STR83##    O M.P. 121-122.degree                                                            . C.                    111 Cl          OCH.sub.3   CH.sub.2 CCH                                                                              CH.sub.3      O n .sub.D.sup.22                                                                1.5619                  112 Cl          OCH.sub.3   CH.sub.2 CCH                                                                               ##STR84##    O M.P. 72-73°                                                             C.                      113 Br          OCH.sub.3   C.sub.2 H.sub.5                                                                            ##STR85##    O M.P. 144.5-145.degr                                                            ee. C.                  114 Br          OCH.sub.3   C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.2 Cl                                                                       O n  .sub.D.sup.19.7                                                             .5685                   115 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.3      O M.P.                                                                           98.5-99.5°                                                              C.                      116 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              O M.P.                                                                           110-111°                                                                C.                      117 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR86##    O M.P. 113-115.degree                                                            . C.                    118 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR87##    O M.P. 94-95°                                                             C.                      119 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CHCH.sub.2                                                                          O M.P.                                                                           89-90° C.        120 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCH  O M.P.                                                                           98.5-99.5°                                                              C.                      121 Cl          OC.sub. 2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                            ##STR88##    O n .sub.D.sup.18.0                                                              1.5172                  122 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR89##    O n .sub.D.sup.19.5                                                              1.5121                  123 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR90##    O M.P. 90-91°                                                             C.                      124 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR91##    O M.P. 120.5-122.degr                                                            ee. C.                  125 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR92##    O n .sub.D.sup.17.0                                                              1.5191                  126 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR93##    O n .sub.D.sup.16.5                                                              1.5186                  127 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR94##    O M.P. 61-62°                                                             C.                      128 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.2 Cl                                                                       O n .sub.D.sup.20.5                                                              1.5466                  129 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR95##    O n .sub.D.sup.18.0                                                              1.5206                  130 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR96##    O n .sub.D.sup.17                                                                1.5140                  131 Cl          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 C N                                                                        O M.P.                                                                           100.5-101.5°                                                             C.                     132 Cl          OC.sub.2 H.sub.5                                                                           CH.sub.2 CHCH.sub.2                                                                        ##STR97##    O M.P. 56-57°                                                             C.                      133 Cl          OC.sub.2 H.sub.5                                                                           CH.sub.2 CHCH.sub.2                                                                        ##STR98##    O n .sub.D.sup.18.5                                                              1.5331                  134 Cl          OC.sub.2 H.sub.5                                                                           CH.sub.2 CCH                                                                               ##STR99##    O n .sub.D.sup.19.5                                                              1.5202                  135 Cl          OC.sub.2 H.sub.5                                                                           CH.sub.2 CHCHCH.sub.3                                                                      ##STR100##   O n .sub.D.sup.22.0                                                              1.5198                  136 Cl          OC.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 Cl                                                                       ##STR101##   O n .sub.D.sup.20.0                                                              1.5323                  137 Br          OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR102##   O M.P. 115.5-116.5.de                                                            gree. C.                138 CH.sub.3    OCH.sub.3   C.sub.2 H.sub.5                                                                            ##STR103##   O M.P. 116.5-118.degr                                                            ee. C.                  139 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.3      O n .sub.D.sup.20.5                                                              1.5212                  140 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              O M.P.                                                                           69-70° C.        141 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR104##   O M.P. 86-87.5.degree                                                            . C.                    142 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR105##   O M.P. 76-77°                                                             C.                      143 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCH  O M.P.                                                                           85.5-86.5°                                                              C.                      144 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR106##   O M.P. 74-75°                                                             C.                      145 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR107##   O M.P. 121-122.5.degr                                                            ee. C.                  146 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR108##   O M.P. 57-59°                                                             C.                      147 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR109##   O n .sub.D.sup.17.5                                                              1.5425                  148 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 OCH.sub.2                                                    CH.sub.2 Cl   O M.P.                                                                           98-99.5°                                                                C.                      149 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR110##   O M.P. 63-64.5.degree                                                            . C.                    150 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR111##   O M.P. 135.5-137.degr                                                            ee. C.                  151 CH.sub.3    OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.Cl                                                                         O n .sub.D.sup.19.5                                                              1.5361                  152 CH.sub.3    OC.sub.2 H.sub.5                                                                           CH.sub.2 CCH                                                                               ##STR112##   O n .sub.D.sup.17.5                                                              1.5112                  153 C.sub.2 H.sub.5                                                                            OCH.sub.3   CH.sub.3                                                                                   ##STR113##   O M.P. 80.5-81.degree                                                            . C.                    154 C.sub.2 H.sub.5                                                                            OCH.sub.3   CH.sub.3   CH.sub.2 C CCH.sub.3                                                                         O n .sub.D.sup.23.2                                                              1.5375                  155 C.sub.2 H.sub.5                                                                            OCH.sub.3   CH.sub.3                                                                                   ##STR114##   O n .sub.D.sup.25.5                                                              1.5092                  156 CHCH.sub.2  OCH.sub.3   CH.sub.3                                                                                   ##STR115##   O M.P. 105.5-107.degr                                                            ee. C.                  157 C.sub.2 H.sub.5                                                                            OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR116##   O M.P. 100-101.degree                                                            . C.                    158 CH.sub.2 CH.sub.2 CH.sub.3                                                                 OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR117##   O M.P. 114-115.degree                                                            . C.                    159 CHCHCH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR118##   O M.P. 89-98°                                                             C.                      160 CHCH.sub.2  OC.sub. 2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                            ##STR119##   O M.P. 127.5-128.5.de                                                            gree. C.                161 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR120##   O M.P. 76-77°                                                             C.                      162 OCH.sub.3   OCH.sub.3   CH.sub.3                                                                                   ##STR121##   O M.P. 121.5-122.5.de                                                            gree. C.                163 OCH.sub.3   OCH.sub.3   C.sub.2 H.sub.5                                                                            ##STR122##   O M.P. 163-164.5.degr                                                            ee. C.                  164 OCH.sub.3   OCH.sub.3   C.sub.2 H.sub.5                                                                           CH.sub.2 CHCHCH.sub.3                                                                        O M.P.                                                                           112.5-113.5°                                                             C.                     165 OCH.sub.3   OCH.sub.3   C.sub.2 H.sub.5                                                                            ##STR123##   O M.P. 138°                                                               C. (decomp.)            166 OCH.sub.3   OC.sub.2 H.sub. 5                                                                          C.sub.2 H.sub.5                                                                            ##STR124##   O M.P. 124-125.degree                                                            . C.                    167 OC.sub.2 H.sub.5                                                                           OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR125##   O M.P. 147-149.degree                                                            . C.                    168 CH.sub.2 OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR126##   O M.P. 107-108.degree                                                            . C.                    169 CH.sub.2 OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR127##   O M.P. 61-66°                                                             C.                      170 CH.sub.2 OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.3                                                                          O M.P.                                                                           79.5-80.5°                                                              C.                      171 CH.sub.2 OCH.sub.2 CHCH.sub.2                                                              OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR128##   O M.P. 68.5-69.degree                                                            . C.                    172 CH.sub.2 OCH.sub.2 CCH                                                                     OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CHCHCH.sub.3                                                                        O n .sub.D.sup.24.0                                                              1.5279                  173 CH.sub.2 OCH.sub.2 CH.sub.2 F                                                              OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.2 Cl                                                                       O n .sub.D.sup.22.5                                                              1.5277                  174 CH.sub.2 OCH.sub.3                                                                         Cl          C.sub.2 H.sub.5                                                                            ##STR129##   O n .sub.D.sup.19.7                                                              1.5221; M.P.                                                                   65-67° C.        175                                                                                 ##STR130## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR131##   O M.P. 116-118.degree                                                            . C.                    176                                                                                 ##STR132## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           CH.sub.2 CHCHCH.sub.2 Cl                                                                     O M.P. 64-65°                                                             C.                      177                                                                                 ##STR133## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR134##   O M.P. 110-111.degree                                                            . C.                    178                                                                                 ##STR135## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR136##   O M.P. 118-119.degree                                                            . C.                    179                                                                                 ##STR137## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR138##   O M.P. 124-125.degree                                                            . C.                    180 CH.sub.2 OCH.sub.3                                                                         CH.sub.3    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              O n .sub.D.sup.17                                                                1.5198                  181 C N         OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR139##   O M.P. 108.5-109.5.de                                                            gree. C.                182 CN          CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR140##   O n .sub.D.sup.20                                                                1.5265                  183 CH.sub.2 CN OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR141##   O M.P. 101-103.degree                                                            . C.                    184 CH.sub.2 CH.sub.2 CN                                                                       OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR142##   O n .sub.D.sup.16.7                                                              1.5089                  185 CHCHCN      OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR143##   O M.P. 97-100°                                                             C.                     186                                                                                 ##STR144## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR145##   O M.P. 103.5-105.degr                                                            ee. C.                  187                                                                                 ##STR146## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR147##   O n .sub.D.sup.17.2                                                              1.5145                  188                                                                                 ##STR148## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR149##   O n .sub.D.sup.17.2                                                              1.5072                  189                                                                                 ##STR150## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR151##   O M.P. 97-99°                                                             C.                      190 CHNOH       OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR152##   O M.P. 172-173.5.degr                                                            ee. C.                  191 CHNOCH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR153##   O M.P. 110-111.5.degr                                                            ee. C.                  192 CCH         OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR154##   O M.P. 154.5-156.degr                                                            ee. C.                  193                                                                                 ##STR155## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR156##   O M.P. 111-121.degree                                                            . C.                    194                                                                                 ##STR157## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR158##   O M.P. 187-192.degree                                                            . C.                    195                                                                                 ##STR159## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR160##   O M.P. 141-143.degree                                                            . C.                    196                                                                                 ##STR161## OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR162##   O M.P. 88-90°                                                             C.                      197 CH.sub.2 OH OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR163##   O M.P. 117-118.degree                                                            . C.                    198 CH.sub.2 OH OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR164##   O M.P. 86-87.5.degree                                                            . C.                    199 CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              S n .sub.D.sup.20                                                                1.5623                  200 CH.sub.3    CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR165##   S M.P. 73.5-75.degree                                                            . C.                    201 OC.sub.2 H.sub.5                                                                           Cl          C.sub.2 H.sub.5                                                                            ##STR166##   S M.P. 70-71.5.degree                                                            . C.                    202 OC.sub.2 H.sub.5                                                                           Cl           C.sub.2 H.sub.5                                                                           ##STR167##   S M.P. 80.5-81.5.degr                                                            ee. C.                  203 OC.sub.2 H.sub.5                                                                           CH.sub.3    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              S M.P.                                                                           84.5-85.5°                                                              C.                      204 OC.sub.2 H.sub.5                                                                           CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR168##   S M.P. 71-72°                                                             C.                      205 OC.sub.2 H.sub.5                                                                           CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR169##   S M.P. 84.5-85.5.degr                                                            ee. C.                  206 CH.sub.3    CH.sub.3    CH.sub.3                                                                                   ##STR170##   O M.P. 67.5-68.5.degr                                                            ee. C.                  207 CH.sub.3    CH.sub.3    CH.sub.3                                                                                   ##STR171##   O n .sub.D .sup.25                                                               1.5269                  208 CH.sub.2 OCH.sub.3                                                                         CH.sub.3    C.sub.2 H.sub.5                                                                            ##STR172##   O n .sub.D.sup.18.5                                                              1.5132; M.P.                                                                   68-69° C.        209 CH.sub.2 OCH.sub.3                                                                         CH.sub.3    C.sub.2 H.sub.5                                                                           CH.sub.3      O n .sub.D.sup.17                                                                1.5219                  210 OCH.sub.3   COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR173##   O M.P. 111-112.degree                                                            . C.                    211 OCH.sub.3   CH.sub.2 CH.sub.2 CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            ##STR174##   O M.P. 75.5-77.degree                                                            . C.                    212 OCH.sub.3   COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR175##   O M.P. 78.5-79.5.degr                                                            ee. C.                  213 OCH.sub.3   CH.sub.2 CH.sub.2 CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            ##STR176##   O M.P. 57-61°                                                             C.                      214 CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR177##   O M.P. 58-61°                                                             C.                      215 CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            ##STR178##   O n .sub.D.sup.19.0                                                              1.5118                  216 CH.sub.2 OCH.sub.3                                                                         CHCH.sub.2  C.sub.2 H.sub.5                                                                            ##STR179##   O n .sub.D.sup.19.0                                                              1.5279                  217 CH.sub.2 OCH.sub.3                                                                         CHCH.sub.2  C.sub.2 H.sub.5                                                                            ##STR180##   O n .sub.D.sup.19.0                                                              1.5327                  218 Br          COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR181##   O M.P. 86.5-88.degree                                                            . C.                    219 Br          COOCH.sub.3 C.sub.2 H.sub. 5                                                                           ##STR182##   O n .sub.D.sup.19.0                                                              1.5363                  220 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                                   ##STR183##   O n .sub.D.sup.18.0                                                              1.5210                  221 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                                   ##STR184##   O n .sub.D.sup.18.0                                                              1.5246                  222 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                                 ##STR185##   O n .sub.D.sup.18.0                                                              1.5108                  223 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                                 ##STR186##   O n .sub.D.sup.18.0                                                              1.5101                  224 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 Cl                                                                       ##STR187##   O n .sub.D.sup.21.0                                                              1.5290                  225 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 Cl                                                                       ##STR188##   O n .sub.D.sup.21.0                                                              1.5317                  226 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 Br                                                                       ##STR189##   O n .sub.D.sup.21.0                                                              1.5425                  227 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 Br                                                                       ##STR190##   O n .sub.D.sup.21.0                                                              1.5421                  228 Br          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR191##   O n .sub.D.sup.17.3                                                              1.5380                  229 Br          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR192##   O n .sub.D.sup.17.3                                                              1.5352                  230 CH.sub.3    COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR193##   O M.P. 78-81°                                                             C.                      231 CH.sub.3    COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR194##   O n .sub.D.sup.23.2                                                              1.5149                  232 Cl          COOCH.sub.3 C.sub.2 H.sub.5                                                                            ##STR195##   O M.P. 82-84°                                                             C.                      233 CH.sub.3                                                                                    ##STR196## C.sub.2 H.sub.5                                                                            ##STR197##   O n .sub.D.sup.25.5                                                              1.5163                  234 CH.sub.3                                                                                    ##STR198## C.sub.2 H.sub.5                                                                            ##STR199##   O n .sub.D.sup.25.5                                                              1.5158                  235 F           OC.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                            ##STR200##   O M.P. 80-83°                                                             C.                      236 OCH.sub.3   OC.sub.2 H.sub.5                                                                           CH.sub. 2 CCH                                                                              ##STR201##   O M.P. 107-109.degree                                                            . C.                    237 OCH.sub.3   OC.sub.2 H.sub.5                                                                           CH.sub.2 CHCH.sub.2                                                                        ##STR202##   O M.P. 93-95°                                                             C.                      238 OCH.sub.3   CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                        ##STR203##   O n .sub.D.sup.25.9                                                              1.5204                  239 OCH.sub.3   CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CCH                                                                               ##STR204##   O n .sub.D.sup.25.9                                                              1.5238                  240 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CF.sub.3                                                                          ##STR205##   O n .sub.D.sup.25.5                                                              1.4919                  241 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                         ##STR206##   O n .sub.D.sup.25.5                                                              1.5160                  242 F           CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR207##   O n .sub.D.sup.29.1                                                              1.4992                  243 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR208##   O n .sub.D.sup.24.6                                                              1.5490                  244 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CCH  O n .sub.D.sup.24.6                                                              1.5373                  245 OCH.sub.3   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR209##   O M.P. 90-91.5.degree                                                            . C.                    246 OCH.sub.3   CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR210##   O n .sub.D.sup.25.2                                                              1.5121                  247 Cl          CH.sub.2 OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                          CH.sub.2 CH.sub.2 F                                                                          O n .sub.D.sup.25.2                                                              1.5245                  248 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR211##   O n .sub.D.sup.25.2                                                              1.5353                  249 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 CCH                                                                        O n .sub.D.sup.25.2                                                              1.5372                  250 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR212##   O n .sub.D.sup.24.0                                                              1.5403                  251 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR213##   S n .sub.D.sup.24.0                                                              1.5534                  252 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR214##   O n .sub.D.sup. 24.0                                                             .5134                   253 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.2 Cl                                                                       O M.P.                                                                           66.5-74°                                                                C.                      254 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR215##   O n .sub.D.sup.24.0                                                              1.5291                  255 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR216##   O n .sub.D.sup.24.0                                                              1.5192                  256 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 CN                                                                         O M.P.                                                                           123-126°                                                                C.                      257 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.3      O n .sub.D.sup.24.0                                                              1.5349                  258 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              O n .sub.D.sup.24.0                                                              1.5295                  259 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR217##   O n .sub.D.sup.24.0                                                              1.5148                  260 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                              S n .sub.D.sup.24.5                                                              1.5648                  261 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CCCH.sub.3                                                                          O n .sub.D.sup.24.5                                                              1.5413                  262 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.2 CHCH.sub.2                                                                          O n .sub.D.sup.24.5                                                              1.5340                  263 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR218##   O n .sub.D.sup.24.5                                                              1.5186                  264 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub. 5                                                                           ##STR219##   O M.P. 72-74°                                                             C.                      265 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR220##   O n .sub.D.sup.24.5                                                              1.5283                  266 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                        ##STR221##   O n .sub.D.sup.25.0                                                              1.5269                  267 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CCH                                                                               ##STR222##   O n .sub.D.sup.25.0                                                              1.5311                  268 Cl          CH.sub.2 OCH.sub.3                                                                         CH.sub.2 CH.sub.2 F                                                                        ##STR223##   O n .sub.D.sup.25.0                                                              1.5133                  269 CH.sub.2 OCH.sub.3                                                                         CH.sub.2 OH C.sub.2 H.sub.5                                                                            ##STR224##   O n .sub.D.sup.24.2                                                              1.5080                  270 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR225##   S n .sub.D.sup.24.2                                                              1.5505                  271 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR226##   O n .sub.D.sup.25.5                                                              1.5270                  272 Cl          CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                            ##STR227##   O n .sub.D.sup.25.5                                                              1.5501                  273 CH.sub.2 OCH.sub.3                                                                          ##STR228## C.sub.2 H.sub.5                                                                            ##STR229##   O n .sub.D.sup.28.5                                                              1.5175                  274 CH.sub.2 OCH.sub.3                                                                          ##STR230## C.sub.2 H.sub.5                                                                            ##STR231##   O M.P. 115-116.degree                                                            . C.                    275 CH.sub.2 OCH.sub.3                                                                          ##STR232## C.sub.2 H.sub.5                                                                            ##STR233##   O M.P. 165-171.degree                                                            . C.                    276 CH.sub.2 OCH.sub.3                                                                          ##STR234## C.sub.2 H.sub.5                                                                            ##STR235##   O M.P. 62-63°                                                             C.                      277 CH.sub.2 OCH.sub.3                                                                          ##STR236## C.sub.2 H.sub.5                                                                            ##STR237##   O n .sub.D.sup.23.5                                                              1.5225                  278 CH.sub.2 OCH.sub.3                                                                          ##STR238## C.sub.2 H.sub.5                                                                            ##STR239##   O n .sub.D.sup.23.5                                                              1.5170                  __________________________________________________________________________

In the practical use of the N-phenylcarbamates (I) as fungicides, they may be applied as such or in a formulation forms such as dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols or flowables. Such formulation form can be prepared in a conventional manner by mixing at least one of the N-phenylcarbamates (I) with an appropriate solid or liquid carrier(s) or diluent(s) and, if necessary, an appropriate adjuvant(s) (e.g. surfactants, adherents, dispersants, stabilizers) for improving the dispersibility and other properties of the active ingredient(s).

Examples of the solid carriers or diluents are botanical materials (e.g. flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw dust, bran, bark powder, cellulose powder, vegetable extract residue), fibrous materials (e.g. paper, corrugated cardboard, old rags), synthetic plastic powders, clays (e.g. kaolin, bentonite, fuller's earth), talcs, other inorganic materials (e.g. pyrophyllite, sericite, pumice, sulfur powder, active carbon) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride).

Examples of the liquid carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methyl naphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc.

Examples of the surfactants are alkyl sulfuric esters, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of the adherents and dispersants may include cesein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar. As the stabilizers, there may be used PAP (isopropyl acid phosphate mixture), TCP (tricresyl phosphate), tolu oil, epoxydized oil, various surfactants, verious fatty acids and their esters, etc.

The foregoing formulations generally contain at least one of the N-phenylcarbamates (I) in a concentration of about 1 to 95% by weight, preferably of 2.0 to 80% by weight. By using the formulations, the N-phenylcarbamates (I) are generally applied in such amounts as 2 to 100 g per 10 are

When only the drug-resistant strains of phytopathogenic fungi are present, the N-phenylcarbamates (I) may be used alone. However, when the drug-sensitive strains are present together with the drug-resistant strains, their alternate use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides or their combined use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides is favorable. In such alternate or combined use, each active ingredient may be employed as such or in conventional agricultural formulation forms. In case of the combined use, the weight proportion of the N-phenylcarbamate (I) and the benzimidazole thiophanate fungicide and/or the cyclic imide fungicide may be from about 1:0.1 to 1:10.0.

Typical examples of the benzimidazole thiophanate fungicides and the cyclic imide fungicides are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     Compound                                                                             Structure            Name                                                __________________________________________________________________________            ##STR240##          Methyl 1-(butylcarbamoyl)benz- imidazol-2-ylcar                                bamate                                              B                                                                                     ##STR241##          2-(4-Thiazolyl)benzimidazole                        C                                                                                     ##STR242##          Methyl benzimidazol-2-ylcarbamate                   D                                                                                     ##STR243##          2-(2-Furyl)benzimidazole                            E                                                                                     ##STR244##          1,2-Bis(3-methoxycarbonyl-2- thioureido)benzene                                O                                                   F                                                                                     ##STR245##          1,2-Bis(3-ethoxycarbonyl-2- thioureido)benzene                                 A                                                   G                                                                                     ##STR246##          2-(O,SDimethylphosphoryl- amino)-1-(3'-methoxyc                                arbonyl-2'- thioureido)benzene                      H                                                                                     ##STR247##          2-(O,ODimethylthiophos- phorylamino)-1-(3'-meth                                oxy- carbonyl-2'-thioureido)benzene                 I                                                                                     ##STR248##          N(3',5'-Dichlorophenyl)-1,2- dimethylcyclopropa                                ne-1,2- dicarboximide                               J                                                                                     ##STR249##          3-(3',5'-Dichlorophenyl)-1-iso- propylcarbamoyl                                imida- zolidine-2,4-dione                           K                                                                                     ##STR250##          3-(3',5'-Dichlorophenyl)-5- methyl-5-vinyloxazo                                lidine- 2,4-dione                                   L                                                                                     ##STR251##          Ethyl (RS)3-(3',5'-dichloro- phenyl)-5-methyl-2                                ,4-dioxo-oxa- zolidine-5-carboxylate                __________________________________________________________________________

In addition, the N-phenylcarbamates (I) may be also used in admixture with other fungicides, herbicides, insecticides, miticides, fertilizers, etc.

When the N-phenylcarbamates (I) are used as fungicides, they may be applied in such amounts as 2 to 100 grams per 10 ares. However, this amount may vary depending upon formulation forms, application times, application methods, application sites, diseases, crops and so on, and therefore, they are not limited to said particular amounts.

Some practical embodiments of the fungicidal composition according to the invention are illustratively shown in the following Examples wherein % and part(s) are by weight.

PREPARATION EXAMPLE 1

Two parts of Compound No. 2, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.

PREPARATION EXAMPLE 2

Thirty parts of Compound No. 15, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.

PREPARATION EXAMPLE 3

Fifty parts of Compound No. 5, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.

PREPARATION EXAMPLE 4

Ten parts of Compound No. 22, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.

PREPARATION EXAMPLE 5

Two parts of Compound No. 107, 88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.

PREPARATION EXAMPLE 6

Thirty parts of Compound No. 54, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.

PREPARATION EXAMPLE 7

Fifty parts of Compound No. 164, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.

PREPARATION EXAMPLE 8

Ten parts of Compound No. 101, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.

PREPARATION EXAMPLE 9

Two parts of Compound No. 44, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.

PREPARATION EXAMPLE 10

Thirty parts of Compound No. 79, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.

PREPARATION EXAMPLE 11

Fifty parts of Compound No. 29, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.

PREPARATION EXAMPLE 12

Ten parts of Compound No. 81, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.

PREPARATION EXAMPLE 13

One part of Compound No. 15, 1 part of Compound No. I, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.

PREPARATION EXAMPLE 14

Two parts of Compound No. 105, 2 parts of Compound No. E, 86 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 4% of the active ingredient.

PREPARATION EXAMPLE 15

Twenty parts of Compound No. 141, 10 parts of Compound J, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.

PREPARATION EXAMPLE 16

Ten parts of Compound No. 181, 40 parts of Compound No. B, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.

PREPARATION EXAMPLE 17

Twenty-five parts of Compound No. 54, 50 parts of Compound I, 18 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 3.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 75% of the active ingredient.

PREPARATION EXAMPLE 18

Twenty parts of Compound No. 105, 30 parts of Compound No. A, 40 parts of powdery sucrose, 5 parts of white carbon, 3 parts of sodium laurylsulfate as a wettig agnet and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.

Typical test data indicating the excellent fungicidal activity of the N-phenylcarbamates (I) are shown below. The compounds used for comparison are as follows:

    ______________________________________                                         Compound             Remarks                                                   ______________________________________                                         Control (a)          Synthesized for                                            ##STR252##          comparison                                                Control (b)          Synthesized for                                            ##STR253##          comparison                                                Control (c)          Synthesized for                                            ##STR254##          comparison                                                Control (d)          Synthesized for                                            ##STR255##          comparison                                                Control (e)          Synthesized for                                            ##STR256##          comparison                                                Control (f)          Synthesized for                                            ##STR257##          comparison                                                Control (g)          Synthesized for                                            ##STR258##          comparison                                                Control (h)          Synthesized for                                            ##STR259##          comparison                                                Control (i)          Agricultural Biological                                    ##STR260##          Chemistry, 35, 1707- 1719 (1971)                          Control (j)          Agricultural Biological                                    ##STR261##          Chemistry, 35, 1707- 1719 (1971)                          Control (k)          Agricultural Biological                                    ##STR262##          Chemistry, 35, 1707- 1719 (1971)                          Control (l)          Agricultural Biological                                    ##STR263##          Chemistry, 35, 1707- 1719 (1971)                          Swep                 Commercially available                                     ##STR264##          herbicide                                                 Chlorpropham         Commercially available                                     ##STR265##          herbicide                                                 Barban               Commercially available                                     ##STR266##          herbicide                                                 CEPC                 Commercially available                                     ##STR267##          herbicide                                                 Propham              Commercially available                                     ##STR268##          herbicide                                                 Chlorbufam           Commercially available                                     ##STR269##          herbicide                                                 Benomyl              Commercially available                                     ##STR270##          fungicide                                                 Thiophanate-methyl   Commercially available                                     ##STR271##          fungicide                                                 Carbendazim          Commercially available                                     ##STR272##          fungicide                                                 Thiabendazole        Commercially available                                     ##STR273##          fungicide                                                 Edifenphos           Commercially available                                     ##STR274##          fungicide                                                 ______________________________________                                    

EXPERIMENT 1

Protective activity test on powdery mildew of cucumber (Sphaerotheca fuliginea):

A flower pot of 90 ml volume was filed with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the following manner, and the results are shown in Table 3.

The leaves examined were measured for a percentage of infected area and classified into the corresponding disease indices, 0, 0.5, 1, 2, 4:

    ______________________________________                                         Disease index Percentage of infected area                                      ______________________________________                                         0             No infection                                                     0.5           Infected area of less than 5%                                    1             Infected area of less than 20%                                   2             Infected area of less than 50%                                   4             Infected area of not less than 50%                               ______________________________________                                    

The disease severity was calculated according to the following equation: ##EQU1##

The prevention value was calculated according to the following equation: ##EQU2##

                  TABLE 3                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             6         200          100       0                                             7         200          100       0                                            13         200           97       0                                            15         200          100       0                                            19         200          100       0                                            20         200          100       0                                            22         200          100       0                                            24         200          100       0                                            28         200           97       0                                            29         200          100       0                                            31         200           94       0                                            32         200           97       0                                            33         200          100       0                                            36         200           97       0                                            39         200           94       0                                            44         200           97       0                                            50         200           97       0                                            51         200          100       0                                            52         200           97       0                                            54         200          100       0                                            55         200          100       0                                            57         200          100       0                                            58         200          100       0                                            59         200          100       0                                            60         200          100       0                                            61         200          100       0                                            62         200          100       0                                            63         200          100       0                                            64         200          100       0                                            65         200          100       0                                            68         200          100       0                                            70         200          100       0                                            71         200          100       0                                            73         200          100       0                                            74         200          100       0                                            77         200          100       0                                            78         200          100       0                                            79         200          100       0                                            80         200          100       0                                            84         200          100       0                                            86         200          100       0                                            88         200           94       0                                            90         200          100       0                                            91         200          100       0                                            92         200           97       0                                            99         200          100       0                                            101        200          100       0                                            102        200          100       0                                            103        200          100       0                                            105        200          100       0                                            109        200          100       0                                            110        200          100       0                                            111        200          100       0                                            112        200          100       0                                            115        200          100       0                                            116        200          100       0                                            117        200          100       0                                            118        200          100       0                                            119        200          100       0                                            120        200          100       0                                            122        200          100       0                                            124        200          100       0                                            127        200          100       0                                            129        200          100       0                                            130        200          100       0                                            131        200          100       0                                            132        200          100       0                                            133        200          100       0                                            134        200          100       0                                            135        200          100       0                                            138        200          100       0                                            140        200          100       0                                            141        200          100       0                                            142        200          100       0                                            143        200          100       0                                            146        200          100       0                                            147        200          100       0                                            152        200          100       0                                            157        200          100       0                                            159        200          100       0                                            165        200          100       0                                            167        200          100       0                                            174        200          100       0                                            181        200          100       0                                            193        200          100       0                                            Control (a)                                                                               200           0        0                                            Control (b)                                                                               200           0        0                                            Control (c)                                                                               200           0        0                                            Control (d)                                                                               200           0        0                                            Control (e)                                                                               200           0        0                                            Control (f)                                                                               200           0        0                                            Control (g)                                                                               200           0        0                                            Control (h)                                                                               200           0        0                                            Control (i)                                                                               200           0        0                                            Control (j)                                                                               200           0        0                                            Control (k)                                                                               200           0        0                                            Control (l)                                                                               200           0        0                                            Swep       200           0        0                                            Chlorpropham                                                                              200           0        0                                            Barban     200           25       0                                            CEPC       200           0        0                                            Propham    200           0        0                                            Chlorbufam 200           0        0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         Carbendazim                                                                               200           0        100                                          ______________________________________                                    

As understood from the results shown in Table 3, the N-phenylkcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the N-phenylcarbamates (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

EXPERIMENT 2

Preventive effect on cercospora leaf spot of sugarbeet (Cercospora beticola):

A flower pot of 90 ml volume was filled with sandy soil, and seeds of sugarbeet (var: Detroit dark red) were sown therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora beticola by spraying. The pot was covered with a polyvinyl chloride sheet to make a condition of high humidity, and cultivation was continued in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 4.

                  TABLE 4                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             6         200           96       0                                             7         200          100       0                                             8         200          100       0                                             13        200           97       0                                             15        200          100       0                                             19        200          100       0                                             20        200          100       0                                             22        200          100       0                                             24        200          100       0                                             28        200           99       0                                             29        200          100       0                                             31        200           94       0                                             32        200          100       0                                             33        200          100       0                                             36        200           97       0                                             38        200           94       0                                             40        200          100       0                                             41        200          100       0                                             44        200           96       0                                             47        200           94       0                                             50        200          100       0                                             51        200          100       0                                             52        200          100       0                                             54        200          100       0                                             55        200          100       0                                             57        200          100       0                                             58        200          100       0                                             59        200          100       0                                             60        200          100       0                                             64        200          100       0                                             68        200          100       0                                             74        200          100       0                                             78        200          100       0                                             79        200          100       0                                             80        200          100       0                                             81        200           96       0                                             86        200          100       0                                             88        200          100       0                                             90        200          100       0                                             91        200          100       0                                             92        200           97       0                                             93        200          100       0                                             99        200          100       0                                            100        200          100       0                                            102        200          100       0                                            104        200          100       0                                            105        200          100       0                                            107        200           97       0                                            108        200          100       0                                            109        200          100       0                                            110        200          100       0                                            112        200          100       0                                            114        200          100       0                                            116        200          100       0                                            117        200          100       0                                            118        200          100       0                                            129        200          100       0                                            131        200          100       0                                            132        200          100       0                                            134        200          100       0                                            138        200          100       0                                            141        200          100       0                                            142        200          100       0                                            143        200          100       0                                            146        200          100       0                                            155        200           94       0                                            157        200          100       0                                            160        200          100       0                                            164        200          100       0                                            168        200          100       0                                            181        200          100       0                                            188        200          100       0                                            193        200          100       0                                            210        200          100       0                                            211        200          100       0                                            214        200          100       0                                            218        200          100       0                                            219        200          100       0                                            224        200          100       0                                            226        200          100       0                                            228        200          100       0                                            229        200          100       0                                            230        200          100       0                                            232        200          100       0                                            233        200          100       0                                            235        200          100       0                                            236        200          100       0                                            237        200          100       0                                            238        200          100       0                                            240        200          100       0                                            242        200          100       0                                            245        200          100       0                                            247        200          100       0                                            256        200          100       0                                            259        200          100       0                                            Control (a)                                                                               200           0        0                                            Control (b)                                                                               200           0        0                                            Control (c)                                                                               200           0        0                                            Control (d)                                                                               200           0        0                                            Control (e)                                                                               200           0        0                                            Control (f)                                                                               200           0        0                                            Control (g)                                                                               200           0        0                                            Control (h)                                                                               200           0        0                                            Control (i)                                                                               200           0        0                                            Control (j)                                                                               200           0        0                                            Control (k)                                                                               200           0        0                                            Control (l)                                                                               200           0        0                                            Swep       200           0        0                                            Chlorpropham                                                                              200           0        0                                            Barban     200           34       0                                            CEPC       200           0        0                                            Propham    200           0        0                                            Chlorbufam 200           0        0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         Carbendazim                                                                               200           0        100                                          ______________________________________                                    

As understood from the results shown in Table 4, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do no show any preventive effect on the tested drug-sensitive strain. To the contrary, commecially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the N-phenylcarbamates (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

EXPERIMENT 3

Preventive effect on scab of pear (Venturia nashicola):

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of pear (var: Chojuro) were sown therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Venturia nashicola by spraying. The resulting plants were placed at 20° C. under a condition of high humidity for 3 days and then at 20° C. under irradiation with a fluorescent lamp for 20 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 5.

                  TABLE 5                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             3         200           94       0                                             5         200           91       0                                             8         200           97       0                                             9         200           96       0                                            10         200           94       0                                            13         200          100       0                                            14         200           91       0                                            15         200          100       0                                            19         200          100       0                                            20         200          100       0                                            22         200          100       0                                            24         200          100       0                                            26         200           91       0                                            27         200           88       0                                            29         200          100       0                                            30         200           88       0                                            31         200          100       0                                            35         200           88       0                                            38         200          100       0                                            42         200           85       0                                            43         200           88       0                                            44         200          100       0                                            45         200           91       0                                            46         200           94       0                                            47         200          100       0                                            48         200           94       0                                            49         200           85       0                                            51         200           94       0                                            53         200          100       0                                            55         200          100       0                                            64         200          100       0                                            65         200          100       0                                            68         200          100       0                                            81         200           97       0                                            87         200           94       0                                            89         200           88       0                                            98         200          100       0                                            100        200          100       0                                            102        200          100       0                                            103        200          100       0                                            104        200          100       0                                            105        200          100       0                                            106        200          100       0                                            107        200           91       0                                            108        200          100       0                                            110        200          100       0                                            112        200          100       0                                            116        200          100       0                                            117        200          100       0                                            118        200          100       0                                            124        200          100       0                                            128        200          100       0                                            132        200          100       0                                            134        200          100       0                                            138        200          100       0                                            141        200          100       0                                            143        200          100       0                                            145        200          100       0                                            146        200          100       0                                            153        200           97       0                                            156        200          100       0                                            163        200          100       0                                            164        200          100       0                                            174        200          100       0                                            181        200          100       0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 5, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 4

Preventive effect on brown leaf-spot of peanut (Cercospora arachidicola):

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of peanut (var: Chiba hanryusei) were sown therein. Cultivation was carried out in a greenhouse for 14 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora arachidicola by spraying. The resulting plants were covered with a polyvinyl chloride sheet to make a humide condition and cultivated in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             6         200          100       0                                             7         200          100       0                                             8         200          100       0                                            10         200          100       0                                            12         200           97       0                                            15         200          100       0                                            19         200          100       0                                            20         200           98       0                                            22         200          100       0                                            24         200           98       0                                            29         200          100       0                                            32         200          100       0                                            36         200          100       0                                            38         200           94       0                                            41         200          100       0                                            44         200           97       0                                            52         200           97       0                                            54         200          100       0                                            55         200          100       0                                            56         200          100       0                                            64         200          100       0                                            68         200          100       0                                            73         200          100       0                                            79         200          100       0                                            80         200          100       0                                            86         200           94       0                                            87         200           91       0                                            88         200          100       0                                            90         200          100       0                                            91         200          100       0                                            92         200          100       0                                            101        200          100       0                                            102        200          100       0                                            105        200          100       0                                            109        200          100       0                                            110        200          100       0                                            117        200          100       0                                            132        200          100       0                                            134        200          100       0                                            138        200          100       0                                            141        200          100       0                                            142        200          100       0                                            146        200          100       0                                            165        200           97       0                                            181        200          100       0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 6, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 5

Preventive effect on gray mold of cucumber (Botrytis cinerea):

Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Botrytis cinerea by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 20° C. for 3 days, the rates of disease severity were observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          1         200           88       0                                             2         200          100       0                                             3         200           94       0                                             4         200           88       0                                             5         200           91       0                                             6         200           96       0                                             7         200          100       0                                             8         200           97       0                                             9         200           91       0                                             10        200           97       0                                             11        200           84       0                                             12        200          100       0                                             13        200           96       0                                             14        200           88       0                                             15        200          100       0                                             16        500           91       0                                             17        500           88       0                                             18        500           88       0                                             19        200          100       0                                             20        200          100       0                                             21        200           97       0                                             22        200          100       0                                             23        200           88       0                                             24        200          100       0                                             25        200           97       0                                             28        200           97       0                                             29        200          100       0                                             31        200            94      0                                             32        200           97       0                                             33        200           88       0                                             34        200           84       0                                             35        200           91       0                                             36        200           97       0                                             37        200           91       0                                             38        200           94       0                                             39        200           94       0                                             40        200           97       0                                             41        200          100       0                                             44        200           94       0                                             47        200           91       0                                             48        200           88       0                                             50        200           94       0                                             51        200           91       0                                             52        200           97       0                                             53        200          100       0                                             54        200          100       0                                             55        200          100       0                                             56        200          100       0                                             57        200          100       0                                             58        200          100       0                                             59        200           97       0                                             60        200          100       0                                             61        200           88       0                                             62        200          100       0                                             63        200          100       0                                             64        200          100       0                                             65        200          100       0                                             66        200          100       0                                             67        200          100       0                                             68        200          100       0                                             69        200          100       0                                             70        200          100       0                                             71        200          100       0                                             72        200          100       0                                              73       200          100       0                                             74        200          100       0                                             75        200          100       0                                             76        200          100       0                                             77        200          100       0                                             78        200          100       0                                             79        200          100       0                                             80        200          100       0                                             81        200           94       0                                             82        200          100       0                                             83        200          100       0                                             84        200          100       0                                             85        200          100       0                                             86        200          100       0                                             88        200           97       0                                             90        200          100       0                                             91        200          100       0                                             92        200           97       0                                             93        200           94       0                                             94        200           97       0                                             95        200           88       0                                             96        200          100       0                                             97        200          100       0                                             98        200           91       0                                             99        200           97       0                                            100        200          100       0                                            101        200          100       0                                            102        200          100       0                                            103        200           97       0                                            104        200          100       0                                            105        200          100       0                                            106        200          100       0                                            107        200           91       0                                            108        200          100       0                                            109        200          100       0                                            110        200          100       0                                            112        200          100       0                                            113        200          100       0                                            114        200          100       0                                            115        200          100       0                                            116        200          100       0                                            117        200          100       0                                            118        200          100       0                                            119        200          100       0                                            120        200          100       0                                            121        200          100       0                                            122        200           88       0                                            123        200          100       0                                            124        200          100       0                                            125        200           94       0                                            126        200           94       0                                            127        200          100       0                                            128        200          100       0                                            129        200          100       0                                            130        200          100       0                                            131        200          100       0                                            132        200          100       0                                            133        200          100       0                                            134        200          100       0                                            135        200          100       0                                            136        200          100       0                                            137        200          100       0                                            138        200          100       0                                            139        200          100       0                                            140        200          100       0                                            141        200          100       0                                            142        200          100       0                                            143        200          100       0                                            144        200          100       0                                            145        200          100       0                                            146        200          100       0                                            147        200          100       0                                            148        200          100       0                                            149        200          100       0                                            150        200          100       0                                            151        200          100       0                                            152        200          100       0                                            153        200           97       0                                            154        200           88       0                                            155        200           91       0                                            156        200           97       0                                            157        200          100       0                                            158        200          100       0                                            159        200          100       0                                            160        200          100       0                                            161        200          100       0                                            162        200          100       0                                            163        200          100       0                                            164        200          100       0                                            165        200          100       0                                            166        200          100       0                                            167        200          100       0                                            168        200          100       0                                            169        200          100       0                                            170        200           94       0                                            171        200          100       0                                            172        200          100       0                                            173        200          100       0                                            174        200          100       0                                            175        200          100       0                                            176        200          100       0                                            177        500           88       0                                            178        500           88       0                                            179        500           88       0                                            180        200          100       0                                            181        200          100       0                                            182        200          100       0                                            183        200          100       0                                            184        200          100       0                                            185        200           95       0                                            186        200           88       0                                            187        200          100       0                                            188        200          100       0                                            189        200          100       0                                            190        200          100       0                                            191        200          100       0                                            192        200          100       0                                            193        200          100       0                                            194        200          100       0                                            195        200          100       0                                            196        200          100       0                                            197        200           97       0                                            198        200           94       0                                            199        200          100       0                                            200        200          100       0                                            201        200          100       0                                            202        200          100       0                                            203        200          100       0                                            204        200          100       0                                            205        200          100       0                                            206        200          100       0                                            207        200           88       0                                            208        200          100       0                                            209        200          100       0                                            210        200          100       0                                            211        200          100       0                                            212        200          100       0                                            213        200          100       0                                            214        200          100       0                                            215        200          100       0                                            216        200          100       0                                            217        200          100       0                                            218        200          100       0                                            219        200          100       0                                            220        200          100       0                                            221        200          100       0                                            222        200          100       0                                            223        200          100       0                                            224        200          100       0                                            225        200          100       0                                            226        200          100       0                                            227        200          100       0                                            228        200          100       0                                            229        200          100       0                                            230        200          100       0                                            231        200          100       0                                            232        200          100       0                                            233        200          100       0                                            234        200          100       0                                            235        200          100       0                                            236        200          100       0                                            237        200          100       0                                            238        200          100       0                                            239        200          100       0                                            240        200          100       0                                            241        200          100       0                                            242        200          100       0                                            243        200          100       0                                            244        200          100       0                                            245        200          100       0                                            246        200          100       0                                            247        200          100       0                                            248        200          100       0                                            249        200          100       0                                            250        200          100       0                                            251        200          100       0                                            252        200          100       0                                            253        200          100       0                                            254        200          100       0                                            255        200          100       0                                            256        200          100       0                                            257        200          100       0                                            258        200          100       0                                            259        200          100       0                                            260        200          100       0                                            261        200          100       0                                            262        200          100       0                                            263        200          100       0                                            264        200          100       0                                            265        200          100       0                                            266        200          100       0                                            267        200          100       0                                            268        200          100       0                                            269        200          100       0                                            270        200          100       0                                            271        200          100       0                                            272        200          100       0                                            273        200          100       0                                            274        200          100       0                                            275        200           88       0                                            276        200          100       0                                            277        200          100       0                                            278        200          100       0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         Thiabendazole                                                                             200           0        100                                          ______________________________________                                    

As understood from the results shown in Table 7, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Thiabendazole show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 6

Preventive effect on gummy stem blight of cucumber (Mycosphaerella melonis):

Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Mycosphaerella melonis by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 25° C. for 4 days, the rates of disease severity were observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 8.

                  TABLE 8                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             6         200          100       0                                             7         200          100       0                                             8         200          100       0                                            10         200          100       0                                            15         200          100       0                                            19         200          100       0                                            20         200          100       0                                            22         200          100       0                                            23         200           91       0                                            29         200          100       0                                            31         200           97       0                                            36         200          100       0                                            39         200           97       0                                            40         200          100       0                                            54         200          100       0                                            56         200          100       0                                            57         200          100       0                                            59         200          100       0                                            64         200          100       0                                            68         200          100       0                                            77         200          100       0                                            78         200          100       0                                            79         200          100       0                                            80         200          100       0                                            86         200          100       0                                            88         200           97       0                                            90         200          100       0                                            91         200          100       0                                            101        200          100       0                                            102        200          100       0                                            105        200          100       0                                            109        200          100       0                                            110        200          100       0                                            117        200          100       0                                            124        200          100       0                                            132        200          100       0                                            134        200          100       0                                            138        200          100       0                                            141        200          100       0                                            142        200          100       0                                            146        200          100       0                                            181        200          100       0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 8, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 7

Preventive effect on green mold of orange (Penicillium italicum):

Fruits of orange (var: Unshu) were washed with water and dried in the air. The fruits were immersed in a solution of the test compound prepared by diluting an emulsifiable concentrate comprising the test compound with water for 1 minute. After drying in the air, the fruits were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Penicillium italicum by spraying and placed in a room of high humidity for 24 days. The degree of damage was determined in the following manner:

The fruits examined were measured for a percentage of infected area and classified into the corresponding indices, 0, 1, 2, 3, 4, 5:

    ______________________________________                                         Disease index Percentage of infected area                                      ______________________________________                                         0             No infection                                                     1             Infected area of less than 20%                                   2             Infected area of less than 40%                                   3             Infected area of less than 60%                                   4             Infected area of less than 80%                                   5             Infected area of not less than 80%                               ______________________________________                                    

Calculation of the degree of damage and the prevention value was made as in Experiment 1.

The results are shown in Table 9.

                  TABLE 9                                                          ______________________________________                                                                 Prevention                                                                               Prevention                                                           value when                                                                               value when                                              Concentration                                                                               inoculated                                                                               inoculated                                              of active    with drug-                                                                               with drug-                                   Compound   ingredient   resistant sensitive                                    No.        (ppm)        strain (%)                                                                               strain (%)                                   ______________________________________                                          2         200          100       0                                             6         200          100       0                                             7         200          100       0                                             8         200          100       0                                            13         200          100       0                                            15         200          100       0                                            19         200          100       0                                            20         200          100       0                                            22         200          100       0                                            24         200          100       0                                            28         200          100       0                                            29         200          100       0                                            36         200          100       0                                            38         200           94       0                                            40         200           97       0                                            51         200          100       0                                            55         200          100       0                                            56         200          100       0                                            64         200          100       0                                            68         200          100       0                                            73         200          100       0                                            78         200          100       0                                            79         200          100       0                                            90         200          100       0                                            99         200          100       0                                            103        200          100       0                                            109        200          100       0                                            110        200          100       0                                            116        200          100       0                                            117        200          100       0                                            118        200          100       0                                            129        200          100       0                                            132        200          100       0                                            134        200          100       0                                            138        200          100       0                                            141        200          100       0                                            146        200          100       0                                            156        200          100       0                                            163        200           94       0                                            181        200          100       0                                            Benomyl    200           0        100                                          Thiophanate-                                                                              200           0        100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 9, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 8

Preventive effect on rice blast (Pyricularia oryzae):

Plastic pots of 90 ml were filled with a cultured soil for rice plants, and seeds of rice plant (var: Kinki No. 33) were sown therein and cultivated in a greenhouse. Onto the seedlings of 3-leaf stage, the test compound formulated in an emulsifiable concentrate and diluted with water was sprayed to enough cover the leaf surfaces with droplets. After air-drying, the seedlings were inoculated with a spore suspension of Pyricularia oryzae by spraying, followed by incubation at 28° C. for 3 days under a high humid condition. The disease severity were observed and the degree of damage was determined in the same manner as in Experiment 1. The results are shown in Table 10.

                  TABLE 10                                                         ______________________________________                                                       Concentration of                                                                            Prevention                                                        active ingredient                                                                           value                                               Compound No.  (ppm)        (%)                                                 ______________________________________                                          28           500          100                                                  46           500          100                                                  47           500          100                                                 101           500          97                                                  153           1000         99                                                  154           1000         95                                                  Edifenphos    500          97                                                  ______________________________________                                    

EXPERIMENT 9

Phytotoxicity to crop plants:

Plastic pots of 150 ml volume were filled with sandy soil, and seeds of wheat (var: Norin No. 61), apple (var: Kogyoku) and peanut (var: Chiba hanryusei) were sown therein. Cultivation was carried out in a greenhouse. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed. After cultivation in the greenhouse for additional 10 days, the phytotoxicity was examined on the following criteria:

    ______________________________________                                         Extent    Observation                                                          ______________________________________                                         -         No abnormality                                                       +         Abnormality due to phytotoxicity observed                                      in a part of crop plants                                             ++        Abnormality due to phytotoxicity observed                                      in entire crop plants                                                +++       Crop plants withered due to phytotoxicity                            ______________________________________                                    

The results are shown in Table 11.

                  TABLE 11                                                         ______________________________________                                                  Concentration                                                                  of active                                                             Compound ingredient  Phytotoxicity                                             No.      (ppm)       Wheat     Apple Peanut                                    ______________________________________                                          2       1000        -         -     -                                          15      1000        -         -     -                                          28      1000        -         -     -                                          39      1000        -         -     -                                          59      1000        -         -     -                                          79      1000        -         -     -                                         102      1000        -         -     -                                         108      1000        -         -     -                                         109      1000        -         -     -                                         110      1000        -         -     -                                         117      1000        -         -     -                                         120      1000        -         -     -                                         141      1000        -         -     -                                         145      1000        -         -     -                                         153      1000        -         -     -                                         Barban   1000        -         ++    ++                                        CEPC     1000        -         ++    ++                                        Swep     1000        ++        ++    +                                         ______________________________________                                    

As understood from the results shown in Table 11, the N-phenylcarbamates (I) of the invention produce no material phytotoxicity, while commercially available herbicides having a chemical structure similar thereto produce considerable phytotoxicity.

EXPERIMENT 10

Preventive effect on powdery mildew of cucumber (Sphaerotheca fuliginea):

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 12.

                  TABLE 12                                                         ______________________________________                                                       Concentration of                                                                            Prevention                                                        active ingredient                                                                           value                                               Compound No.  (ppm)        (%)                                                 ______________________________________                                          2            100           36                                                  2             20           0                                                   15           100           32                                                  15            20           0                                                   22           100           44                                                  22            20           0                                                   54           100           28                                                  54            20           0                                                   59           100           36                                                  59            20           0                                                  105           100           28                                                 105            20           0                                                  110           100           32                                                 110            20           0                                                  117           100           36                                                 117            20           0                                                  141           100           28                                                 141            20           0                                                  181           100           44                                                 181            20           0                                                  A             100           45                                                 A              20           12                                                 B             500           42                                                 B             100           10                                                 C             100           42                                                 C              20           8                                                  D             500           36                                                 D             100           0                                                  E             100           44                                                 E              20           10                                                 F             100           43                                                 F              20           8                                                  G             100           42                                                 G              20           8                                                  H             100           40                                                 H              20           5                                                  2 +      A        20 +  20     100                                             2 +      F        20 + 20      100                                             15 +     A        20 + 20      100                                             15 +     F        20 + 20      100                                             22 +     A        20 + 20      100                                             22 +     B        20 + 20      100                                             22 +     C        20 + 20      100                                             22 +     D        20 + 20      100                                             54 +     G        20 + 20      100                                             54 +     H        20 + 20      100                                             59 +     A        20 + 20      100                                             59 +     B        20 + 20      100                                             59 +     E        20 + 20      100                                             59 +     F        20 + 20      100                                             105 +    A        20 + 20      100                                             105 +    E        20 + 20      100                                             110 +    E        20 + 20      100                                             110 +    F        20 + 20      100                                             117 +    G        20 + 20      100                                             117 +    H        20 + 20      100                                             141 +    A        20 + 20      100                                             141 +    B        20 + 20      100                                             181 +    A        20 +  20     100                                             181 +    B        20 + 20      100                                             181 +    E        20 + 20      100                                             181 +    F        20 + 20      100                                             ______________________________________                                    

As understood from the results shown in Table 12, the combined use of the N-phenylcarbamates (I) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.

EXPERIMENT 11

Preventive effect on gray mold of tomato (Botrytis cinerea):

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of tomato (var: Fukuji No. 2) were sown therein. Cultivation was carried out in a greenhouse for 4 weeks. Onto the resulting seedlings at the 4-leaf stage, the test compound(s) formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Botrytis cinerea by spraying and placed at 20° C. in a room of high humidity for 5 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 13.

                  TABLE 13                                                         ______________________________________                                                       Concentration of                                                                            Prevention                                                        active ingredient                                                                           value                                               Compound No.  (ppm)        (%)                                                 ______________________________________                                          2            100           42                                                  2             20           0                                                   15           100           32                                                  15            20           0                                                   22           100           38                                                  22            20           0                                                   54           100           40                                                  54            20           0                                                   59           100           32                                                  59            20           0                                                  105           100           38                                                 105            20           0                                                  110           100           40                                                 110            20           0                                                  117           100           38                                                 117            20           0                                                  141           100           42                                                 141            20           0                                                  181           100           28                                                 181            20           0                                                  I             100           48                                                 I              20           22                                                 J             100           46                                                 J              20           18                                                 K             100           42                                                 K              20           15                                                 L             100           42                                                 L              20           12                                                 2 +      I        20 + 50      100                                             2 +      J        20 + 50      100                                             2 +      K        20 + 50      100                                             2 +      L        20 + 50      100                                             15 +     I        20 + 50      100                                             15 +     K        20 + 50      100                                             22 +     I        20 + 50      100                                             22 +     L        20 + 50      100                                             54 +     I        20 + 50      100                                             54 +     J        20 + 50      100                                             59 +     I        20 + 50      100                                             59 +     K        20 + 50      100                                             105 +    I        20 + 50      100                                             105 +    J        20 + 50      100                                             110 +    I        20 + 50      100                                             110 +    J        20 + 50      100                                             117 +    I        20 + 50      100                                             117 +    K        20 + 50      100                                             141 +    I        20 + 50      100                                             141 +    J        20 + 50      100                                             181 +    I        20 + 50      100                                             181 +    K        20 + 50      100                                             ______________________________________                                    

As understood from the results shown in Table 13, the combined use of the N-phenylcarbamates (I) of the invention with benzimidazole thiphanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use. 

What is claimed is:
 1. A N-phenylcarbamate compound selected from the group consisting of:Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)-carbamate; Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)-carbamate; Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)-carbamate; Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)-carbamate; Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)-carbamate; Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate; Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate; Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)-carbamate; Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)-carbamate; Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)-carbamate; Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)-carbamate; Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate; Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate; Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)-carbamate; Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)-carbamate; Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)-carbamate; and Isopropyl N-[3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]-carbamate.
 2. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
 3. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)carbamate.
 4. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)carbamate.
 5. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)carbamate.
 6. The N-phenylcarbmate according to claim 1, which is Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
 7. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate.
 8. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate.
 9. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)carbamate.
 10. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
 11. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
 12. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)carbamate.
 13. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate.
 14. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate.
 15. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)carbamate.
 16. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)carbamate.
 17. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)carbamate.
 18. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]carbamate.
 19. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of a compound of claim
 1. 